Catalysts



UNITED STATE PATENT OFFICE CATALYSTS Vladimir N. Ipatiefl' and Louis Schmerling, Chi- 09.30, 111., assignors to Universal Oil Products Company, Chicago, 111., a corporation of Delaware No Dawn... Application May 14, 1942,

1 Serial No. 443,008

1 The resent invention is concerned with catalysts which are useful in accelerating the rates 'of various types of hydrocarbon conversion reactions such as cracking of heavy hydrocarbon mixtures to produce lower-boiling motor fuel I fractions, treating motor fuels toincrease their antiknock rating, isomerizing paraflln or naphthene hydrocarbons, alkylating aromatics or isoparafilns with olefins and alternative alkylating agents, polymerization of unsaturated hydrocarbons .to form higher molecular weight polymers and other reactions.

Various types of catalysts are employed both for accelerating the reaction rates inthe types of conversion mentioned and for altering their course in the direction of increased yields of desired products. Such catalysts are or many types and include metals, metal oxides, salts and spe-, cial composites prepared for use in particular conversion reactions. The present invention is concerned with novel types of catalysts which are utilizable in a wide variety of different hydrocarbon conversions so that in' general their utility is greater than that of many other types of catalysts.

In one speciflc'embodiment the present invention relates to a catalyst for hydrocarbon cona number of Friedel-Crafts type metal halides which may be interacted, a considerable number of alternative catalysts can be made although they win-not necessarily be equivalent in their action in catalyzing'any particular type of hydrocarbon reaction. The phosphoric acids which may be used in preparing the catalyst of this invention include ortho-phosphoric acid, pyrophosphoric acid and meta-phosphoric acid.

Friedel-Crafts metal halides which are reacted with'the phosphoric acids to form useful hydrocarbon conversion catalysts in accordance with the present invention include such salts as aluminum chloride, aluminum bromide, zinc chloride, zirconium chloride, ferric chloride, antimony chloride, bismuth chloride, and others. Aluminum chloride is as a rule the most generally utilized Friedel-Crafts catalystin hydrocarbon conversion reactions of the types mentioned as its 12 Claims. (01. ass-228.2)

' those described in connection with ortho-phos .2 i activity is usually higher than those of other members of the groupunder agiven set of conditions. However, disadvantages attend its use in some instances on account of its high degree of activity. Thus, it requires handling in the absence of water since it is readily hydrolyzed and ultimatelyloses itsv catalytic activity when hydrolyzed beyond a. certain point. In reactions such as polymerization wherein higher boiling polymers are formed from lower molecular weight olefins, there is a tendency for it to form hydrocarbon-aluminum chloride complexes rather than to form polymers and when elevated temperatures are employed, there is an increased tendency for undesirable decompositions to occur. By reacting proportioned mixtures of aluminum halides and phosphoric acids in accordance with the present invention, the activities of such catalysts are modified and different hydrocarbon conversions may be more accurately controlled.

Catalytic materials formed by the interaction of ortho-phosphoric acid and aluminum chloride typify the present invention. For example, in forming such a catalyst, equimolal proportions of ortho-ph'osphoric acid and finely divided substantially anhydrous aluminum chloride may be mixed and reaction brought about by heating the mixture to a temperature of about C. at which point a vigorous evolution of hydrogen chloride takes place and a pale yellowish powder is left which apparently contains a compound having the formula C1zA1OPO(OH)2 in admixture withunreacted aluminum chloride. This 'composite material has definite catalytic activity in hydrocarbon conversion reactions. When the mixture of phosphoric acid and aluminum chloride is heated at temperatures substantially higher than'80 C., more hydrogen chloride is evolved and, as a rule, the catalytic activity of the composites decreases if more than one mole of hydrogen chloride based on the aluminum chloride is formed when approximately equimolar mixtures of the phosphoric acid and the aluminum chloride are used.- When proportionately larger amounts of aluminum chloride are mixed with the phosphoric acid, composites having generally highercatalytic activities may be produced which may owe their increased activity to the presence of uncombined aluminum chloride.

Composite catalytic materials analogous to phoric acid and aluminum chloride can be made by reacting other phosphoric acids with aluminum chloride or with other metal halides'such as those already mentioned assbeing catalysts .of-. the

. Eriedel -craftatype." The catalytic activity of these alternative materials may vary considerably from those-of high activity made from aluminum chloride or aluminum bromide and phosphoric 'icids t oitho se having catalytic activity df aloWerorder-more suitable for less difligijilfiiyrc atlyaable readtidfis. Furthermore, some of=thse materialsmay be active catalysts for certainreact'ions and less active for others. Not all of them necessarilyexert their maximumcatalytic activity under identical conditionshaving regard for any given reaction.

Catalysts of the present type. areutiiizable in powdered form in suspension in hydrocarbons as a slurry when hydrocarbons are being isomerized or allwlated under liquid or mixed phase conditions and may be used in both batch or continuous processes. Iii contrast to aluminum halide catalysts they do not form any substantial amounts of complexes with unsaturated hydrocarbons so that they 'may be used in continuous Exampic I A catalyst was madeby intimately mixing at ordinary temperatures equimolar proportions of 100 per cent ortho-phosphoric acid and finely divided aluminum chloride and heating gradually to a temperature of 80 C. until the evolution of hydrogen chloride ceased. The residual material was a pale yellowish powder.

That this catalyst was active for the alkylation 01' benzene wasshown by adding 5 parts by weight of the catalyst to a mhzture of 80 parts by weight of benzene and 21 parts by weight of propylene in a pressure vessel in which the added 'agsofctosi tially in excess of Initial boiling point to it 'GIIIIIIIIIIIII I III IIII 4 hydrocarbons were produced which had the following boiling range characteristics:

Volume Oondensible at 4a 0 95-125 0 126-150 0. Rnsidnn zeoatxi ea K The boiling rangd of products indicates that a considerable yield,,of alkylated products was formed, particularly in respect to fractions boilins between 75 and 125 C. which constituted about 25 per cent by'. volume of the liquid products.

Example III Using the prepared catalyst, heptane was isomerized at 100 C. to produce a 20 percent volume yield of isoheptanes. In'the test a sample of a commercial heptane having an octane number of 57.9 was heated for 4 hours in the presence of the catalyst at a temperature of 100 C. The octane number of the recovered liquid was found to be 61.2.

We claim as our invention: 1 a

l. A process for the manufacture of a catalyst which comprises mixing an uminum halide and a phosphoric acid selected from the group consisting of ortho, meta and pyro phosphoric acids and heating to cause interaction of the acid and the aluminum halide and to evolve a substantial amount of hydrogen halide but not substanone mol based on the aluminum halide. L

materials were stirred for a period of 4 hours at 25 C. 97 parts/by weight of liquid product'was formed which had the following distillation characteristics:

Frau-flun- Volume per cent 125-145" C Mil-163 O- 163-2)0 O Residue an l n Example II The catalyst prepared as described above was also active for the alkylation of isobutane with propene'. 85 parts by weight of isobutane, 20 parts by weight of propylene, 4 parts by weight of hy-- 2. A process for the manufacture of a catalyst which comprises heating a. substantially equimolal mixture of ortho-phosphoric acid and substantially anhydrous aluminum chloride to a temperature of about'80 C. until about one mol of hydrogen chloride is evolved, and discontinuing said heating when about one mol of hydrogen chloride has been evolved.

3. A process for the manufacture of a catalyst which comprises forming a substantially equimolar mixture of an aluminum halide and a phosphoric acid selected from the group consisting of said aluminum chloride and to evolve a substandrogen chloride and 10 parts of the catalyst were added to a pressure vessel and the contents were maintained at a temperature of C. for a period which comprises forming a mixture of an alumi num halide and a phosphoric acid selected from the group consisting of ortho, meta and pyro phosphoric acids .in which the aluminum halide is in molar excess in. respect tothe phosphoric acid and heating to cause interaction of said acid and said aluminum halide and to evolve hydrogen halide in an amount not substantially in excess of one mol based on the aluminum halide.

6. A process for the manufacture of a. catalyst which comprises forming a mixture of a. phosphoric acid selected from the group consisting of ortho, meta and pyro phosphoric acids and aluminum chloride in which the aluminum chloride.

is in molar excess in respect to the phosphorid acid and heating to cause interaction of said acid and said aluminum chloride and to evolve hydrogen chloride in an amount not substantially in excess of one mol based on the aluminum chloride. '7. The solid reaction product of a. substantially anhydrous aluminum halide with a phosphoric acid selected from the group consisting. of ortho, meta and pyro phosphoric acids,'said product resulting from the heating of the aluminum halide and the phosphoric acid sufllciently toevolve a substantial amount of hydrogen halide but not substantially in excess of one mol based on the aluminum halide. v

ii. The solid reaction product of substantially anhydrous aluminum chloride with a phosphoric acid selected from the group consisting of ortho, meta and pyro phosphoric acids, said product resulting from the heating of the aluminum chloride and the phosphoric acid sufliciently to evolve a substantial amount of hydrogen chloride but not substantially in excess of one molhesed on the aluminum chloride.

9. The solid reaction product of a substantially anhydrous aluminum halide with ortho-phos- V I v 6 phoric acid, said product resulting from the heating of the aluminum halide and the phosphoric acid suiiiciently to evolve a substantial amount of hydrogen halide but not substantially in excess tially anhydrous aluminum halide with pyrophosphoric acid, said product resulting from the heating of the aluminum halide and the phosphoric acid sufliciently to evolve a substantial amount of hydrogen halide but not'substantially l in excess of one mol based on the aluminum halide.

12. The solid reaction product of substantially anhydrous aluminum chloride with pyro-phosphoric acid, said product resulting from the heating of the aluminum chloride and the phosphoric acid sumciently to evolve a substantial amount of hydrogen chloride but not substantially in excess of one mol based on the aluminum chloride.

vmnm N. IPA'I'IEFF. LOUIS SCI-WW6.- 

